CN102107911A - Method for preparing ferrous sulfate by reducing iron mud under induction action of solution discharge plasma - Google Patents
Method for preparing ferrous sulfate by reducing iron mud under induction action of solution discharge plasma Download PDFInfo
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- CN102107911A CN102107911A CN 201110052855 CN201110052855A CN102107911A CN 102107911 A CN102107911 A CN 102107911A CN 201110052855 CN201110052855 CN 201110052855 CN 201110052855 A CN201110052855 A CN 201110052855A CN 102107911 A CN102107911 A CN 102107911A
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- solution
- iron
- ferrous sulfate
- iron mud
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Abstract
The invention relates to a method for preparing ferrous sulfate by reducing iron mud under the induction action of solution discharge plasma, which comprises the following steps: adding iron mud into a reaction kettle, slowly adding sulfuric acid while stirring so as to dissolve the iron mud; adding an organic reducing agent or industrial waste liquor thereof into the obtained solution; transferring the obtained solution into a solution discharge plasma reactor containing a cathode and an anode; switching on the power, raising the voltage to 500-800V and the current to 5-20A, discharging to react for 20-30 minutes; filtering the solution in the reactor to remove insoluble impurities; and concentrating the filtrate to crystallize, thereby obtaining ferrous sulfate heptahydrate or ammonium ferrous sulfate hexahydrate. In the invention, the raw material has wide sources and is sufficient, and the reducing agent can be replaced by industrial organic waste liquor, thereby indirectly treating the organic waste liquor pollution; and the method can effectively recover iron atoms in the iron mud, and thus, can not result in the problems of iron mud accumulation and the like in the process.
Description
Technical field
The present invention relates to a kind of preparation method of ferrous sulfate, be specially the method for utilizing industrial waste iron mud to produce ferrous sulfate for reductive agent by the solution discharge for organism such as raw material and phenol.
Background technology
Ferrous sulfate is an important chemical material, is widely used in water treatment coagulant, catalyzer and fodder additives etc.Conventional ferrous sulfate production method can be reacted by iron filings and dilute sulphuric acid and be obtained or produced by ilmenite that by product obtains in the titanium white production.
Ferrous sulfate in use generally all is converted into iron mud (except the fodder additives) directly or indirectly.For example Fenton reagent is the effective ways of handling organic wastewater with difficult degradation thereby
[1-2]In acidic medium, H
2O
2Under the effect of ferrous sulfate, produce the hydroxyl radical free radical of strong oxidizing property, with the organic pollutant oxygenolysis in the waste water.Ferrous sulfate becomes ferric iron in reaction process, with medium furnishing alkalescence (generally using calcium hydroxide), final iron was with ironic hydroxide (iron mud) sedimentary form and aqueous phase separation after reaction finished.Owing to often be mingled with impurity such as toxic substance and calcium sulfate in these iron mud, reclaim difficulty, generally be dropped.The iron mud that abandons can make soil block, and pH changes, and causes soil pollution.The report that at present relevant iron mud is recycled is seldom: people such as Cao Ruijun
[3]A kind of acid catalysis and clay method that is equipped with ferrous sulfate and ferrous ammonium sulphate of iron powder reducing iron utilized disclosed; People such as Li Mali
[4]Studied and utilized the clay technology that is equipped with ferrous sulfate monohydrate of iron powder reducing iron.The main drawback of above-mentioned technology is all to utilize iron powder to make reductive agent.On the one hand present iron powder price comparison height increases production cost; On the other hand since iron powder add affiliation make every production once back iron total amount increase by 1/3rd, the ferrous sulfate of increase can not intra-company's digestion and can only be sold toward the elsewhere, because problems such as scale cause transportation cost to increase.
The objective of the invention is to propose a kind of method of utilizing organism (or industrial effluent) such as phenol to produce ferrous sulfate for ferric iron in the reductive agent reduced iron mud.The reductive agent that uses in the process is as organism but not iron powder, can make like this ferrous sulfate in recycling process, do not increase iron total amount, reductive agent is cheap and easy to get simultaneously, can bring good economic benefit and social benefit.
Reference:
[1]Neyens?E.，Baeyens?J.A?review?of?classic?Fenton’s?peroxidation?as?an?advanced?oxidation?technique，J.Hazard.Mater.2003，98：33-50
[2]Pignatello?J.J.，Oliveros?E.，Mackay?A.Advanced?oxidation?processes?for?organic?contaminant?destruction?based?on?the?Fenton?reaction?and?related?chemistry，Critical?Rev.Environ.Sci.Technol.2006，36：1-84
[3] Cao Ruijun, plum winter, a kind of method of producing ferrous sulfate and ferrous ammonium sulphate, CN 1138009A
[4] Li Mali, Yu Changyan utilizes the research of the clay feed grade ferrous sulfate monohydrate of scrap iron, Hunan chemical industry, 1997,27:32-40
Summary of the invention
The objective of the invention is to reclaim the deficiency of technology, propose a kind of solution discharge plasma and induce ferric iron in the organism reduced iron mud to prepare the method for ferrous sulfate at conventional iron mud.Purpose of the present invention realizes by following scheme:
A kind of scrap iron mud solution discharge plasma prepares the method for ferrous sulfate, may further comprise the steps:
(1) in reactor, adds iron mud; The sulfuric acid that under agitation slowly adds concentration and be 1-5mol/L pH value of solution 1-4 to the reactor makes the dissolving of iron mud;
(2) in step (1) gained solution, add organic reducing agent;
(3) step (2) gained solution is transferred in the solution discharging plasma reactor that contains anodic-cathodic; Connect power supply, improve voltage to 500-800V, electric current 5-20A, exoelectrical reaction 20-30 minute;
(4) solution in step (3) reactor is filtered, remove insoluble impurity; Gained filtrate condensing crystal obtains iron vitriol or six aqueous ferrous sulfate ammoniums;
Ironic hydroxide content is 80wt.%～100wt.% in the described iron mud of step (1);
The described organic reducing agent of step (2) is a kind of in technical pure phenol, aniline or the oil of mirbane, or contains above-mentioned organic industrial effluent; When described organic reducing agent was technical pure phenol, aniline or oil of mirbane, its add-on was 10% of an iron shale amount; When described organic reducing agent was industrial effluent, organic content was 1-3wt.% in the waste liquid, and the industrial effluent add-on is counted 10% (quality that is phenol, aniline or oil of mirbane in the industrial effluent that is added be iron shale amount 10%) of iron shale amount with organism;
The described condensing crystal of step (4): regulate pH＜1 when add 1-5mol/L sulfuric acid in filtrate, condensing crystal gets iron vitriol (FeSO
47H
2O); When add the ammonium sulfate powder that is equivalent to iron shale amount 15% in filtrate, condensing crystal gets six aqueous ferrous sulfate ammonium (FeSO
4(NH
4)
2SO
4.6H
2O).
Described power supply is high-voltage DC power supply or high-voltage dc pulse power, its output voltage at 0V between the 1000V.
The discharge electrode material of described solution discharging plasma reactor is a kind of in gold, platinum, titanium or the nichrome.
Described solution discharging plasma reactor inner anode is a discharge electrode, and the cathode area in the plasma reactor is 2-10000 with the ratio of annode area: 1.
When the anode glow of solution discharging plasma reactor of the present invention discharges, ferric iron is in the solution discharge plasma in the iron mud, by the reductibility particle of discharge generation and organic free radical reduction, final production ferrous sulfate (ferrous ammonium sulphate) and carbonic acid gas, react suc as formula following (is reductive agent with phenol):
28Fe (OH)
3+ C
6H
5OH+28H
2SO
4+ 99H
2O+ discharge → 28FeSO
47H
2O+6CO
2↑
28Fe (OH)
3+ C
6H
5OH+28H
2SO
4+ 28 (NH
4)
2SO
4+ 71H
2O+ discharge → 28FeSO
4(NH
4)
2SO
4.6H
2O+6CO
2↑
Compare with existing technology, the present invention has following advantage:
1. raw material sources are extensive; Use organism to replace traditional iron powder as reductive agent, the industrial organic waste liquid in also available pharmaceutical factory or chemical plant replaces organism as reductive agent, and the raw material abundance has been administered the organic liquid waste pollution simultaneously indirectly.
2. technology is simple, and the reaction conditions gentleness need not catalyzer, and the reaction times is short.
3. production process energy efficiency height, cost are low.
4. the iron atom in can efficient recovery iron mud can not cause in the process problems such as iron is more and more.
Embodiment
The invention will be further described by following embodiment, but embodiments of the invention are not limited only to this.Among the embodiment
Embodiment 1
With platinum is solution discharging plasma reactor anode material, and the anode electrode area is 1: 100 with the ratio of cathode electrode area.With phenol is reductive agent, prepares iron vitriol according to the following steps.
(1) in the 100L reactor, adds 10.0 kilograms in dried iron mud (ironic hydroxide content 94%);
(2) under agitation slowly add the sulphuric acid soln that concentration is 1.0mol/L, make pH value of solution between 2.0-2.5;
(3) in process (2) solution, add 1.0 kilograms of technical pure phenol, stirring and dissolving;
(4) solution of step (3) gained is transferred in the solution discharge reactor that contains anodic-cathodic;
(5) connect power supply, improve voltage to 500V, electric current 15-20A reacted 20 minutes;
(6) solution in the reactor in the step (5) is filtered, remove insoluble impurity;
(7) solution that obtains in step (6) adds 1mol/L H
2SO
4, make pH value of solution＜1, solution is carried out evaporative crystallization, obtain 21.7 kilograms of iron vitriol products, productive rate 89%.
Embodiment 2
With platinum is solution discharging plasma reactor anode material, and the anode electrode area is 1: 500 with the ratio of cathode electrode area.With aniline is reductive agent, is prepared iron vitriol according to the following steps.
(1) in the 100L reactor, adds 10.0 kilograms in dried iron mud (ironic hydroxide content 94%);
(2) under agitation slowly add the sulphuric acid soln that concentration is 2mol/L, make pH value of solution between 1-3;
(3) in process (2) solution, add 1 kilogram of technical pure aniline, stirring and dissolving;
(4) solution of step (3) preparation is transferred in the solution discharge reactor that contains anodic-cathodic;
(5) connect power supply, improve voltage to 550V, electric current 15-20A, 30 minutes reaction times;
(6) solution in the reactor in the step (5) is filtered, remove insoluble impurity;
(7) solution that obtains in step (6) adds 1mol/L H
2SO
4, make pH value of solution＜1, solution is carried out evaporative crystallization, obtain 22.2 kilograms of iron vitriols, productive rate 91%.
Embodiment 3
With the gold is solution discharging plasma reactor anode material, and the anode electrode area is 1: 1000 with the ratio of cathode electrode area.With industrial phenol waste liquid is reductive agent, carries out iron mud solution plasma discharging system ferrous sulfate according to the following steps.
(1) in the 100L reactor, adds 10.0 kilograms in mud of iron (ironic hydroxide content 91%);
(2) under agitation slowly add the sulphuric acid soln that concentration is 5mol/L, make pH value of solution between 2.5-3.0;
(3) in step (2) solution, add 50 kilograms of 2% industrial phenol waste liquids of phenol content (being that phenol is 1 kilogram in the waste liquid), stirring and dissolving;
(4) solution with step (3) preparation places the solution discharge reactor that contains anodic-cathodic;
(5) connect power supply, improve voltage to 600V, electric current 15-20A, 25 minutes reaction times;
(6) solution in the reactor in the step (5) is filtered, remove insoluble impurity;
(7) solution that obtains in step (6) adds 5mol/L H
2SO
4, make pH value of solution＜1, solution is carried out evaporative crystallization, obtain 20.3 kilograms of iron vitriols, productive rate 86%.
Embodiment 4
With the nichrome is solution discharging plasma reactor anode material, and the anode electrode area is 1: 1000 with the ratio of cathode electrode area.With phenol is reductive agent, carries out iron mud solution plasma discharging system iron vitriol according to the following steps.
(1) in the 100L reactor, adds 10 kilograms in mud of iron (ironic hydroxide content 96%);
(2) under agitation slowly add the sulphuric acid soln that concentration is 3mol/L, make pH value of solution between 1-4;
(3) in process (2) solution, add 1 kilogram of technical pure phenol, stirring and dissolving;
(4) solution with step (3) preparation places the solution discharge reactor that contains anodic-cathodic;
(5) connect power supply, improve voltage to 600V, electric current 15-20A, 30 minutes reaction times;
(6) solution in the reactor in the step (5) is filtered, remove insoluble impurity;
(7) solution that obtains in step (6) adds 5mol/L H
2SO
4, make pH value of solution＜1, to the capable evaporative crystallization of solution, obtain 20.7 kilograms of iron vitriols, productive rate 83%.
Embodiment 5
With platinum is solution discharging plasma reactor anode material, and the anode electrode area is 1: 500 with the ratio of cathode electrode area.With phenol is reductive agent, carries out iron mud solution plasma discharging system ferrous ammonium sulphate according to the following steps.
(1) in the 100L reactor, adds 10 kilograms in mud of iron (ironic hydroxide content 94%);
(2) under agitation slowly add the sulphuric acid soln that concentration is 2.5mol/L, make pH value of solution between 1-4;
(3) in process (2) solution, add 1 kilogram of technical pure phenol, stirring and dissolving;
(4) solution with step (3) preparation places the solution discharge reactor that contains anodic-cathodic;
(5) connect power supply, boosted voltage is to 600V, and electric current 15-20A reacted 20 minutes;
(6) solution in the reactor in the step (5) is filtered, remove insoluble impurity;
(7) solution that obtains in the step (6) is added 1.5 kilograms in ammonium sulfate powder, condensing crystal gets six aqueous ferrous sulfate ammonium (FeSO
4(NH
4)
2SO
4.6H
2O) 31.9 kilograms, productive rate 90.4%.
Claims (4)
1. a solution discharge plasma induces the reduction of iron mud to prepare the method for ferrous sulfate, may further comprise the steps:
(1) in reactor, adds iron mud; The sulfuric acid that under agitation slowly adds concentration and be 1-5mol/L pH value of solution 1-4 to the reactor makes the dissolving of iron mud;
(2) in step (1) gained solution, add organic reducing agent;
(3) step (2) gained solution is transferred in the solution discharging plasma reactor that contains anodic-cathodic; Connect power supply, improve voltage to 500-800V, electric current 5-20A, exoelectrical reaction 20-30 minute;
(4) solution in step (3) reactor is filtered, remove insoluble impurity; Gained filtrate condensing crystal obtains iron vitriol or six aqueous ferrous sulfate ammoniums;
Ironic hydroxide content is 80wt.%～100wt.% in the described iron mud of step (1);
The described organic reducing agent of step (2) is a kind of in technical pure phenol, aniline or the oil of mirbane, or contains above-mentioned organic industrial effluent; When described organic reducing agent was technical pure phenol, aniline or oil of mirbane, its add-on was 10% of an iron shale amount; When described organic reducing agent was industrial effluent, organic content was 1-3wt.% in the waste liquid, and the industrial effluent add-on is counted 10% of iron shale amount with organism;
The described condensing crystal of step (4): regulate pH＜1 when add 1-5mol/L sulfuric acid in filtrate, condensing crystal gets iron vitriol; When add the ammonium sulfate powder that is equivalent to iron shale amount 15% in filtrate, condensing crystal gets six aqueous ferrous sulfate ammoniums.
2. solution discharge plasma according to claim 1 induces iron mud reduction to prepare the method for ferrous sulfate, it is characterized in that described power supply is high-voltage DC power supply or high-voltage dc pulse power, its output voltage at 0V between the 1000V.
3. solution discharge plasma according to claim 1 induces iron mud reduction prepare the method for ferrous sulfate, and the anode material that it is characterized in that described solution discharging plasma reactor is a kind of in gold, platinum, titanium or the nichrome.
4. solution discharge plasma according to claim 3 induces the reduction of iron mud to prepare the method for ferrous sulfate, it is characterized in that described solution discharging plasma reactor inner anode is a discharge electrode, the cathode area in the plasma reactor is 2-10000 with the ratio of annode area: 1.
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|---|---|---|---|
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|---|---|---|---|
| CN2011100528555A CN102107911B (en) | 2011-03-04 | 2011-03-04 | Method for preparing ferrous sulfate by reducing iron mud under induction action of solution discharge plasma |
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| CN102107911B CN102107911B (en) | 2012-07-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100528555A Expired - Fee Related CN102107911B (en) | 2011-03-04 | 2011-03-04 | Method for preparing ferrous sulfate by reducing iron mud under induction action of solution discharge plasma |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104261622A (en) * | 2014-09-29 | 2015-01-07 | 中国电建集团中南勘测设计研究院有限公司 | Fenton sewage treatment process and equipment thereof |
| CN105836987A (en) * | 2016-05-25 | 2016-08-10 | 浙江奇彩环境科技股份有限公司 | Method for resource utilization of Fenton iron mud |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4036941A (en) * | 1976-04-08 | 1977-07-19 | American Cyanamid Company | Preparation of ferric sulfate solutions |
| CN1100700A (en) * | 1994-07-13 | 1995-03-29 | 西安交通大学 | Method for prodn. of polymeric ferrous sulphate solution |
| CN1138009A (en) * | 1996-03-28 | 1996-12-18 | 西安交通大学 | Method for production of ferrous sulfate and ferrous ammonium sulfate |
| WO2006061127A1 (en) * | 2004-12-07 | 2006-06-15 | Tronox Pigments Gmbh | Method for the reduction of the soluble chromate concentration in cement, and preparation comprising cement and water-soluble metal sulfates |
| CN101514033A (en) * | 2009-03-21 | 2009-08-26 | 山东军辉建设安装工程有限公司 | Environment friendly processing method of waste acid containing ferrous sulphate |
-
2011
- 2011-03-04 CN CN2011100528555A patent/CN102107911B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4036941A (en) * | 1976-04-08 | 1977-07-19 | American Cyanamid Company | Preparation of ferric sulfate solutions |
| CN1100700A (en) * | 1994-07-13 | 1995-03-29 | 西安交通大学 | Method for prodn. of polymeric ferrous sulphate solution |
| CN1138009A (en) * | 1996-03-28 | 1996-12-18 | 西安交通大学 | Method for production of ferrous sulfate and ferrous ammonium sulfate |
| WO2006061127A1 (en) * | 2004-12-07 | 2006-06-15 | Tronox Pigments Gmbh | Method for the reduction of the soluble chromate concentration in cement, and preparation comprising cement and water-soluble metal sulfates |
| CN101514033A (en) * | 2009-03-21 | 2009-08-26 | 山东军辉建设安装工程有限公司 | Environment friendly processing method of waste acid containing ferrous sulphate |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104261622A (en) * | 2014-09-29 | 2015-01-07 | 中国电建集团中南勘测设计研究院有限公司 | Fenton sewage treatment process and equipment thereof |
| CN105836987A (en) * | 2016-05-25 | 2016-08-10 | 浙江奇彩环境科技股份有限公司 | Method for resource utilization of Fenton iron mud |
| CN105836987B (en) * | 2016-05-25 | 2019-04-02 | 浙江奇彩环境科技股份有限公司 | A kind of method of Fenton iron cement resource utilization |
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|---|---|
| CN102107911B (en) | 2012-07-04 |
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